Time-dependent electron transfer and energy dissipation in condensed media

Area of Science:

• Surface science
• Physical chemistry
• Condensed matter physics

Background:

• Understanding electron and energy transfer is crucial for electrochemical processes.
• The Newns-Anderson-Schmickler model is a key framework for studying adsorbate-electrode interactions.
• Solvent effects and adsorbate dynamics significantly influence charge transfer.

Purpose of the Study:

• To investigate electron and energy transfer dynamics for a moving adsorbate on a metal electrode in a solvent.
• To analyze the impact of adsorbate motion, solvent coupling, and electrode potential on transfer processes.
• To develop an analytical expression for the average energy transfer rate.

Main Methods:

• Utilizing the time-dependent Newns-Anderson-Schmickler model Hamiltonian.
• Employing a semiclassical trajectory treatment for the adsorbate.
• Applying the Keldysh Green's function scheme for theoretical analysis.

Main Results:

• Electron transfer is non-adiabatically suppressed due to adsorbate motion and coupling with solvent phonons.
• Energy dissipation occurs through electron-hole pair excitations.
• Solvent modes hinder, while electrode potential facilitates, energy dissipation.

Conclusions:

• Adsorbate motion and solvent interactions play a critical role in suppressing electron transfer.
• Energy transfer is a complex process influenced by both solvent dynamics and external electrical fields.
• An analytical expression for the energy transfer rate in the slow-motion limit was derived, providing theoretical insights.